Ab initiorate coefficients for reactions of 2,5-dimethylhexyl isomers with O₂: temperature- And pressure-dependent branching ratios

Chemical kinetics of O₂-addition to alkyl radicals (R), termed first O₂-addition in the oxidation mechanism of alkanes, are of central importance to next-generation combustion strategies designed for operations in the low- to intermediate-temperature region (<1000 K). In the present work, stationary points on potential energy surfaces (PES), temperature- and pressure-dependent rate coefficients, and branching fractions of product formation from R + O₂reactions initiated by the addition of molecular oxygen (³O₂) to the three alkyl radicals of a branched alkane, 2,5-dimethylhexane, are reported. The stationary points were determined utilizingab initio/DFT methods and the reaction energies were computed using the composite CBS-QB3 method. Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) calculations were employed to compute rate coefficients, from which branching fractions were determined over the pressure range of 10⁻³-20 atm and the temperature range of 400-900 K on three different surfaces. The quantum chemistry results reveal several distinct features. For the addition of O₂to the tertiary alkyl radical 2,5-dimethylhex-2-yl, the most energetically favorable channel leads to the formation of 2,2,5,5,-tetramethyl-tetrahydrofuran, a cyclic ether intermediate formed coincident with OH in a chain-propagating step from the decomposition of tertiary-tertiary hydroperoxyalkyl (QOOH). On the R + O₂surface of the secondary radical, 2,5-dimethylhex-3-yl, the pathways for the formation of methyl-propanal + iso-butene + OHviaconcerted C-C and O-O bond scission of tertiary QOOH and that of cyclic ether + OH are the most energetically favorable pathways. The R + O₂surface for the reaction of the primary radical, 2,5-dimethylhex-1-yl, reveals two competitive chain-propagation channels, leading to 2-iso-propyl-4-methyl-tetrahydrofuran + OH and 2,2,5-trimethyltetrahydropyran + OH. Below 100 Torr, the formation of the aforementioned species dominates the respective total R + O₂rate coefficient, while at pressures above 1 atm collisionally stabilized alkylperoxy (ROO) dominates at the temperatures considered here. The results of this study are in very good agreement with the experimentally measured intermediates and products of the 2,5-dimethylhexyl radical + O₂reaction.